US3923826A - Synthesis of 5-(beta-methylmercaptoethyl)-hydantoin - Google Patents
Synthesis of 5-(beta-methylmercaptoethyl)-hydantoin Download PDFInfo
- Publication number
- US3923826A US3923826A US480277A US48027774A US3923826A US 3923826 A US3923826 A US 3923826A US 480277 A US480277 A US 480277A US 48027774 A US48027774 A US 48027774A US 3923826 A US3923826 A US 3923826A
- Authority
- US
- United States
- Prior art keywords
- reaction
- methylmercaptoethyl
- hydantoin
- caustic alkali
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- SBKRXUMXMKBCLD-UHFFFAOYSA-N 5-(2-methylsulfanylethyl)imidazolidine-2,4-dione Chemical compound CSCCC1NC(=O)NC1=O SBKRXUMXMKBCLD-UHFFFAOYSA-N 0.000 title abstract 2
- 230000015572 biosynthetic process Effects 0.000 title description 9
- 238000003786 synthesis reaction Methods 0.000 title description 9
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 239000003518 caustics Substances 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims abstract 5
- 238000000034 method Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229940091173 hydantoin Drugs 0.000 claims description 11
- AKLOIDCXSWPTQW-UHFFFAOYSA-N 2-sulfanylbutanal Chemical compound CCC(S)C=O AKLOIDCXSWPTQW-UHFFFAOYSA-N 0.000 claims description 10
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012736 aqueous medium Substances 0.000 claims description 5
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000004470 DL Methionine Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 235000006109 methionine Nutrition 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
Definitions
- ABSTRACT 5-(fi-methylmercaptoethyl) hydantoin is synthesized in a good yield by reacting B-methylmercaptopropionaldehyde with hydrogen cyanide and a C0 and NH source selected from the group consisting of ammonium bicarbonate. ammonium carbonate and a mixture of carbon dioxide and ammonia in the presence of a caustic alkali.
- the reaction requires a longer period of time greater than 5 hours at a temperature below 70C. If the reaction temperature is raised to above 80C to shorten the reaction time, a side reaction will unavoidably take place so that the reaction mixture darkens remarkably. The side reaction decreases both the quality and the yield of S-(B-methylmercaptoethyl)-hydantoin and, therefore, is undesirable for practicing the synthesis on a large scale.
- the above and other objects are achieved by reacting B-methylmercaptopropionaldehyde with hydrogen cyanide and a C and NH source selected from the group consisting of ammonium bicarbonate, ammonium carbonate, and a mixture of carbon dioxide and ammonia in the presence of a caustic alkali.
- a C and NH source selected from the group consisting of ammonium bicarbonate, ammonium carbonate, and a mixture of carbon dioxide and ammonia
- the preferable range of molar ratios of the reatants based on the molarity of B-methylmercaptopropionaldehyde is: l to 2 for hydrogen cyanide, l to 3 moles for the CO and NH source, and 0.1 to 2 moles for the caustic alkali.
- suitable caustic alkali are sodium hydroxide, potassium hydroxide and lithium hydroxide.
- the caustic alkali is not effective and the use of the same in amounts exceeding 2 moles causes polymerization of the aldehyde.
- the reaction may preferably be carried out in an aqueous medium such as water, aqueous methanol, aqueous ethanol and the like.
- the reaction proceeds sufficiently at a temperature of about 50C to 90C.
- the reaction time varies with the reaction temperature, as usual, but is generally 1 to 3 hours. Excessive reaction times will not result in any severely adverse effect. For example, the reaction will be substantially complete within 2 hours at about 80C.
- reaction mixture thus obtained may be utilized without isolation and further purification in obtaining DL-methionine. Since the present invention makes it possible to use hydrogen cyanide as the cyanogen source of the synthesis, this method is economically more advantageous than the prior method using sodium cyanide.
- EXAMPLE 1 28g of ammonium bicarbonate, 10g of sodium hydroxide, 24g of [-l-methylmercaptopropionaldehyde and 146g of water are charged in a 500 ml capacity flask having'a stirring means.-7g of hydrogen cyanide is added to the flask at 10C with stirring. The mixture is then stirred at C for 2 hours.
- the resulting reaction mixture is a homogeneous, clear, pale-yellow liquid.
- the yield of S-(B-methylmercaptoethyl) hydantoin is 97% based on B-methylmercaptopropinaldehyde.
- EXAMPLE 2 25g of ammonium carbonate, 9g of sodium hydroxide and 134g of water are charged in a 500 ml capacity flask having a stirring means. 7g of hydrogen cyanide and 22g of B-methylmercaptopropionaldehyde are added to the flask successively with stirring while the temperature is kept at 10C. The mixture is stirred at 80C for 2 hours.
- the resulting reaction mixture is a homogeneous, clear, pale-yellow liquid.
- the yield of S-(B-methylmercaptoethyl) hydantoin is 98% based on B-methylmercaptopropionaldehyde.
- caustic alkali 19g of ammonium carbonate and 100g of water are charged in a 300 ml capacity flask of the same type. 5g of hydrogen cyanide and 17g of ,B-methylmercaptopropinaldehyde are added to the flask successively while the mixture is maintained at 10C. The mixture not containing caustic alkali is stirred at 80C for 2 hours.
- the resulting reaction mixture is a heterogeneous, cloudy, brown liquid containing partly separated oily substances.
- the yield of S-(B-methylmercaptoethyl) hydantoin is 81% based on B-methylmercaptopropionaldehyde.
- a method of synthesizing S-(B-methylmercaptoethyl) hydantoin which comprises reacting B-methylmercaptopropionaldehyde with reactants consisting essentially of, per mole of B-methylmercaptopropionaldehyde, l-2 moles of hydrogen cyanide and 1-3 moles of a C0 and NH source selected from the group consisting of ammonium bicarbonate, ammonium carbonate and and a mixture of carbon dioxide and ammonia in the presence of 0.1-2 moles of a caustic alkali.
- tion is carried out in an aqueous medium.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP48070168A JPS5018467A (pt) | 1973-06-20 | 1973-06-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3923826A true US3923826A (en) | 1975-12-02 |
Family
ID=13423734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US480277A Expired - Lifetime US3923826A (en) | 1973-06-20 | 1974-06-17 | Synthesis of 5-(beta-methylmercaptoethyl)-hydantoin |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3923826A (pt) |
| JP (1) | JPS5018467A (pt) |
| ES (1) | ES427408A1 (pt) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8002172A (nl) * | 1980-04-15 | 1981-11-16 | Shell Int Research | Reactor voor exotherme reacties. |
| JPS5969138A (ja) * | 1982-10-09 | 1984-04-19 | ユ−オ−ピ−・インコ−ポレ−テツド | 触媒の再生方法およびそれに使用する装置 |
| DE19547236A1 (de) | 1995-12-18 | 1997-07-03 | Degussa | Verfahren zur Herstellung von D,L-Methionin oder dessen Salz |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2480644A (en) * | 1946-10-31 | 1949-08-30 | Merck & Co Inc | Preparation of dl-valine |
| US2612521A (en) * | 1951-07-09 | 1952-09-30 | Du Pont | Alpha-amino,4, 6, 6-trimethyl heptanoic acid |
| US2999863A (en) * | 1953-07-27 | 1961-09-12 | Univ Oklahoma State | Alpha-phthalimido-acetamide derivatives |
-
1973
- 1973-06-20 JP JP48070168A patent/JPS5018467A/ja active Pending
-
1974
- 1974-06-17 US US480277A patent/US3923826A/en not_active Expired - Lifetime
- 1974-06-19 ES ES427408A patent/ES427408A1/es not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2480644A (en) * | 1946-10-31 | 1949-08-30 | Merck & Co Inc | Preparation of dl-valine |
| US2612521A (en) * | 1951-07-09 | 1952-09-30 | Du Pont | Alpha-amino,4, 6, 6-trimethyl heptanoic acid |
| US2999863A (en) * | 1953-07-27 | 1961-09-12 | Univ Oklahoma State | Alpha-phthalimido-acetamide derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5018467A (pt) | 1975-02-26 |
| ES427408A1 (es) | 1976-07-16 |
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